Manufacture of saturated hydrocarbon materials



C. J. ENGLE Aug. 21, 1951 MANUFACTURE OF' SATURATED HYDROCARBON MATERIALS F'iled Nov. 19, 1948 A TTORNEYS Patented Aug. 21,v 1951 UNITED GFF IC El MANUFAozrUItEeoF sA'rURArrlmHYDRO-l Y oARBoN MATERIALS,r charles Jllinjgle, Bartlesville, Okla., assignor to; l ll'liillios Petroleum Company; oosp'oratoioe Delaware Application November 19, 1948,- SerlialNo. 60H07u 1. This invention relates to' hydrogen transfer'. In one aspect this invention relates toi the' facture of" paraiin'i-c hydiocarlons` from` the oonresponding vvole'ns.` In'anoill'erv aspect:l this l'- vention relates to 'the use of a' novel hydrogen donor in a4 hydrogentransier step.

Various compounds are known which contain combined' hydrogen in an unstall statef of" com.-

Vloination at high' temperatures, and"manyofv these as tetralin, lcommercial decalin, hydrogenated' anthracene, and thelike;

This invention is concerned.withf-themanufact'urel of `sat`urated`hydrocarhons from unsaturated hydrocarbon materials by a hydrogen transfer method employing a new andI novel' hydrogen donor.' v

An ob'ject'ofthi's invention srto providelaprocess for the manufacture of saturated hydroear'.- bon materials;

Another object sto` provide a.procession the manufacture of" paraflin hydrocarbons fromA oleviin hydrocarbons, by: hydrogenY transfer1 Another Objectis to provid afhydrogen trans,- ferprocess wherein a new andnovel. hydrogen donor is'utilized;

Another object is to provide ya process for the manu-facture of an isoparain from a n-olen.

the art,.. from.- the` accompanying disc'aussiont andv disclosure. s Y

In vaccordance with my invention, unsaturated hydrocarbonma'terialsareconverted to more saturated materials in. a--hydrogen transfer process utilizing cis decalin as :a hydrogen donor.

I have discovered that cis decalin is a much more liberalv donor in hydrogen transfer reactions than is trans-decalm; and-thatfif^insteadof"enii ploying commercialdecalin,A whichn is miiitre of cis and trans compounds containing-a" large proportion lof I transV -decali-n, IA employ cis" decali'n, Il' obtain hydrogen-transfer vofgreatly'7 improved eiilcieney Gisisdecalin for use in the practice of. my invention may-beobtained from any source? How- 11 Glainsi' (01.2665467873165C 2" even, coin'menciail decaln' serves as a suitable sourceoff cisde'calin for' use'in theV practiceof my invention. Whenutilizing commerciallde'ca'linin this Wam I have" found" thaty when removing only a part of the` trans isomer, I-` obtain a hydrogen donor more' 'al'otiv'e than' 'the commercial dec'alin', although thernost active donor' is obtained-'when the trans" isomorisoompltelyfremoved. Unsatuite'd hydrocarbon materials that may b'ec'onvetted" to compoundsjof higher saturation' inl aofcordance with' my invention include" normally gaseous'- olens; light olefin" hydrocarbons', or pentenes, hexenes; heptenes', and the like', and heavier unsaturated." components of distillat's, suoli asof'gas'-oilsandthelilze Mixtures o'ivsilc'h olons' as those speoinoally mentioned herein', may' be oonvrte'd tlipl'ac'ticeof rnyinverltin. In" Order to" present n'iy"inventionA more" clearly, reference isniade tothe'attachedngurei W'hiohis a' diagrammatic' representation ofl 'apparatus Whifcll can b'eused'ithepractiCeUfa preferred embodimentoffmy'irivention. 1t is tobeuncler'- Stood that the is" diag'ralnlnatic alld that Vario'usmodcationsmay loe made' and still r'emain withinrne' scope-of-rny invention: Referr'i'ng to` meneur@ ois'- deoaiin from" line ln" and recycled* cis decain from lines'V `I1l and" l2; each hereaftefdescrihed; are" passed through line I3 tod reaotor' rr containing a nxod oedof' a silicametal oxide catalyst comprising from 1 toper ce'llt all'lliil'aj; de'st'lill'dIii0Ie":flJ.11y'liieljfterj t0- getherfwithhydroearhoncharge from 'line 'l hoorn"- prisingfesn' lontane feedJ stock' from" line i 6l and recycled butenes from line 'lj'lide'scribed hereafter. ISIIaoeial"siiff-lines l 3and' l Sare' passezrto reactor l 4' a respeotivo-imoleratio within" me limits of abolitl 035:"1" toz'l''pretferajblyl ahout -llzl Space velocities of fresh feed and cis decalinare" each inv`r theo'rclelf=of"aiool'itl 100 to 600 gas volm'es per catalyst volume per: hour;l Catalyst in" reaction zone l 4-- ismain-tained at' temperature' in me range Ufffoln i325' tot L''Ci' Pressulsinfzr'i'e Miare' maintained" uslllllly"v athl'lo'slilieri'', although subatmospheric or elevated" p're'ss'l'ire'sf` mayA be utilized', Totaljemiieritfrom reactor wis' passed throughcline* I 8 Jto'`s(epijreiti'oi nl'eansA l 9 comprising coolers separators, distillation equipment, str'ag' tanksf'a tiilik", not individually illustitedfV whichfc'afoeuset' effect a' Separation of varinsprodutTractins contained in the maftel'fials"inflii'ie"I8.y In'separation zone I'B, reacted donor: oo'riionsifi'gjtetalin, Cintia, anoloi naphtlalene Ci`oI-`, `and anyunreateddonor, are sepf aretedfroi' eh otherV and froindthe totalveffl'en't, Unie' "i'donnif e. CioHia, comprises cisdec'alin, so'rnetiy es having been'pai'tiallyfis'omerizeolf' in zone" |11 to' the" trans isomer; depend ingforr the 'temperature and'pe'ssjro, conditions therein; and;rocycie'd'tnrougnilines 221' 2'3; ll anda-l sito"iPact-orAA le: wneirit contains notrans 3 isomer. When any trans isomer is present, material in line 22 is passed through lines 24 and 26 to fractionation Zone 21 wherein cis decalin and trans decalin are separated, cis decalin being passed `as bottoms product therefrom through lines 28, l I and I3 to reactor I4, and trans decalin being passed `as overhead product through lines 29 and 3l to further utilization, not shown. However, it may be preferable, depending upon the amount of trans isomer overhead in line 29, to convert the trans decalin to the cis isomer. Accordingly, when it is desired to Aconvert, trans decalin from line 29 to the cis isomer, materials from line 29 may be passed through line 32 to dehydrogenation zone 33 and therein heated at a dehydrogenating temperature, usually in the range of 200 to 400 C. in the presence of a suitable dehydrogenation catalyst such as, chromia, bauxite, and the like, to form tetralin and/or naphthalene. I9 is passed through line 2l and 'admixed in line 36 with dehydrogenation product from zone 33 passed through line 94, and the resulting `admix- Reacted donor, separated in zone ture regenerated, i. e., rehydrogenated in hy- Y tionation zone 21 when it contains any trans decalin, and in the absence of any trans decalin, material in line 38 is passed through lines l2 and I3 and recycled to reactor I4. Any unreacted portion of olens, introduced through line I6 to reactor I4, is separated in zone I9 and recycled therefrom to zone I4 through line I1. From zone I9 is withdrawn isobutane through line 4I and normal butane lthrough line 42 -as products of the process.

If desired, a donor fraction containing both reacted donor and unreacted donor may be separated in zone I9 and passed to regeneration zone 3'1 through lines 20 and 36.

Commercial decalin may be utilized as a source of -cis decalin or of make-up cis decalin, as desired, `by its introduction to fractionation zone 21 through line 113.

For convenience and clarity certain apparatus such as pumps, surge tanks, accumulators, valves,

etc. have not been shown in the drawing. Obviously, such modifications of the present invention may be practiced without departing from the scope of the invention.

' Preferably, silica-metal oxide catalysts are employed in the hydrogen transfer process of my invention.

I may employ a silica-metal oxide type catalyst prepared by first forming a hydrous acidic silica gel by adding an alkali silicate toan excess of an acid, washing soluble material from resulting gel, treating or `activating the gel with an 'aqueous solution of a suitable metal and subsequently washing and drying the treated material. In this manner, a part of the metal, presumably in the form of a hydrous oxide, or loose hydroxide compound formed by hydrolysis is selectively adsorbed by the hydrous silica, and is not removed by subl sequent washing. The most often used catalyst of this type, at present, is a silica-alumina catalyst, prepared by treating a wet or partially dried hydrous silica gel =with an aluminuri salt solution vandjsubsequently washing and drying the treated material. However, catalysts of a very similar nature, vbut differing among themselves as to one or more specific properties, may be prepared by using, instead of an aluminum salt, a hydrolyzable salt of a metal selected from group III B or from group IV A of the periodic system and may be referred to in general as silica-metal oxide type catalysts. As listed in Modern Inorganic Chemistry by J. W. Mellor (Longmans, Green & Co. (1939), revised and edited by G. D. Parkes) on page 118 group lII B consists of boron, aluminum, gallium, indium and thallium, and group IV A consists of titanium, zirconium, hafnium `and thorium. More particularly, salts of indium and thallium in addition to aluminum in group III'B may be used, `ami salts of titanium, zirconium and thorium in group IV A may be used to treat silica gel and to prepare catalysts of this general type.

Another feature of my invention is a concomitant isomerization to produce the more highly branched saturated hydrocarbon products, the extentV of isomerization depending on the specific olefin charge stock and the catalyst employed. For example, when feeding isobutene and employing a silica-alumina type catalyst containing as high as 25 per cent alumina, a very small amount of normal butane isomerization product is formed. However, when feeding a normal butene and employing a silica-alumina type catalyst of high silica content, extensive isomerization takes place and the product contains signiiicantly high yields of isobutane.

My invention is illustrated by the following examples. 'Ihe reactants, their proportions, vand other specific ingredients fare presented as being typical and should not Abe construed to limit the invention unduly.

Example I Mole per cent Propane andiighr 2.6 Butanes-butenes 95.4 Pentanes and heavier 2.0

Total 100.0

The butanes-butenes fraction had the following composition:

` Mole per cent `Iso-butane 29.3 n-Butane 0.2 l Iso-butene 65.1 Butene-l 2.0 Trans-butene-Z 2.0 Cis-butene-Z 1.4

rot-ai 100.0

Of the total isobutene charged, 22.4 per cent was asoma.:

ed material, Apassing efliuent from the zone of said catalyst and resolving same| into a parain hydrocarbon-rich fraction and a fraction containing reacted donor, in a regeneration step passing said fraction containing reacted donor to a hydrogenation zone and therein regenerating said reacted donor by hydrogenation, recovering cis decalin as a product of said regeneratingy recycling cis decalin regeneration product to said ycatalyst zone, separating said paraffin hydrocarbon-rich fraction into a normally gaseous parafin fraction and a fraction containing unreacted olen, recycling said unreacted olen to said catalyst Zone, and recovering a parafn hydrocarbon as a product `of the process.

5. The process of claim 4 wherein said normally gaseous olen comprises a butene and said paraffin comprises isobutane.

6. The process of claim 4 wherein said olefin is butene-2, said catalyst contains from 1 to 25 per cent alumina and said paraffin comprises isobutane.

7. The process of claim 4 wherein said olen is isobutene, said catalyst contains from 20 to 30 per cent alumina and said paraiin comprises isobutane.

8. In a hydrogen transfer process employing an isomeric mixture of decalins as a hydrogen donor in the conversion of an olen hydrocarbon to a paraffin hydrocarbon, the improvement comprising recovering a hydrogen donor consisting essentially of cis decalin from said isomeric mixture, and employing the donor thus recovered as the sole donor in said conversion.

9. In a hydrogen transfer process employing an isomeric mixture of decalins as a hydrogen donor in the conversion of an olen hydrocarbon to a parain hydrocarbon, the improvement comprising removing trans isomer from said isomeric mixture and employing resulting residual decalin as said donor.

10. A continuous process for the manufacture of isobutane from isobutene, comprising passing isobutene together with a hydrogen donor consisting essentially of cis` decalin in a mol ratio of said isobutene to said donor in the range of 0.5:1 to 5:1, through a xed bed of a synthetic silicaalumina as a catalyst maintained at a temperalture in the range of 325 to 400 C., at a space velocity of said isobutene and said donor each withdonor and said isobutane-rich fraction containing unreacted isobutene, passing said donor fraction to a hydrogenation zone and therein regenerating said reacted donor by hydrogenation, recovering cis decalin from the total product of said regeneration, recycling cis decalin thus recovered to said catalyst zone, separating isobutene from said isobutane-rich fraction and recycling isobutene thus recovered to said catalyst zone, and recovering isobutane as a product of the process.

11. A continuous process for the manufacture of isobutane from n-butene, comprising passing n-butene together with a hydrogen donor consisting essentially of cis decalin, in a mol ratio of said n-butene to said donor in the range of 0.5:1 to 5:1, through a xed bed of a synthetic silica-alumina as a catalyst maintained at a temperature in the range of 325 to 400 C., at a space .velocity of said n-butene and said donor each within the range of to 600 gas Volumes per Volume of catalyst per hour, passing eiiluent from the zone of said catalyst, recovering an isobutane'- rich fraction and a donor-rich fraction from said eluent, said donor-rich fraction containing reacted donor and said isobutane-rich fraction `containing unreacted n-butene, passing said donor fraction to a hydrogenation Zone and therein regenerating said reacted donor by hydrogenation recovering cis decalin from the total product of said regeneration, recycling cis decalin thus recovered to said catalyst zone, separating n-butene from said isobutane-rich fraction and recycling n-butene thus recovered to said catalyst zone, and recovering isobutane as a product of the process.

CHARLES J. ENGLE.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,241,393 Danner May 13, 1941 2,328,755 Thomas Sept. 7, 1943 2,472,254 Johnson June 6, 1949 FOREIGN PATENTS Number Country Date 846,480 France June 5, 1939 OTHER REFERENCES Miall, Dictionary of Chemistry, 2nd ed. 1949), 

1. THE METHOD OF MANUFACTURING A PARAFFIN HYDROCARBON FROM AN OLEFIN HYDROCARBON BY HYDROGEN TRANSFER FROM A HYDROGEN DONOR, COMPRISING HEATING SUCH AN OLEFIN HYDROCARBON IN ADMIXTURE WITH A HYDROGEN DONOR CONSISTING ESSENTIALLY OF CIS DECALIN, IN THE PRESENCE OF A SILICA-METAL OXIDE CATALYST AT A TEMPERATURE AT WHICH THE COMBINATION OF HYDROGEN IN SAID DONOR COMPOUND IS UNSTABLE AND AT LEAST A PORTION OF SAID DONOR BECOMES SPENT TO FORM A CORRESPONDING NAPHTHALENE CONTAINING AT LEAST 8 AND NOT MORE THAN 12 HYDROGEN ATOMS PER MOLECULE, AND RECOVERING A RESULTING PARAFFIN HYDROCARBON AS A PRODUCT OF THE PROCESS. 